Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions

Definitions

• the field of the invention contemplated herein pertains to the safening of enhanced herbicidal phytotoxicity induced by the interaction with various biocides, especially insecticides.
• the safening action is effected by the presence of various antidotal (safener) compounds.
• herbicidal compositions may contain other additaments such as fertilizers, biocides, e.g., insecticides, fungicides, nematicides, etc., herbicide antidotes, etc.
• Additional agricultural practices include the application of said herbicidal compositions to soils or vegetation previously treated with said biocides.
• major problems can arise as a result of the interaction of herbicides and various biocides, particularly various insecticides and/or fungicides.
• the common result of such interaction is the enhancement of the phytoxic activity of the herbicide in various crops.
• This enhanced phytotoxicity is referred to in the literature and will be so used herein as "negative synergy/synergism" between the herbicide(s) and the biocide(s).
• negative synergism is expressed in terms or decreased emergence of a crop, reduced crop survival or vigor, crop stand reduction and/or crop yield.
• the herbicides and biocides giving rise to negative synergy when in contact with each other have been found to include members from a variety of classes, including, but not limited to, in the case of herbicides, sulfonylureas, imidazolinones, aliphatic and aromatic carboxylic acids, amides salts and esters, isoxazolidinones, ureas, triazines, thiocarbamates, acetanilides, etc., etc.
• organic phosphates organic phosphates
• OPs organic phosphates
• carbamates organic phosphates
• pyrethroids cyclopropanecarboxylic acid esters
• carboxamides dicarboximides
• perchlorocyclohane etc.
• Negative synergism has been found to occur between herbicides and insecticides in a variety of crops including small grain crops, narrow leaf crops, e.g., corn, rice, barley, sorghum, wheat and broadleaf crops such as cotton, soybeans and sugarbeets.
• Chambers et al involved a variety of types of pesticides, including as herbicides fluometuron, diuron and norea ureas; CIPC (a carbamate); DCPA (a terephthalate); prometryne (a triazine); trifluralin (a dinitrotoluidine) and nitralin (an aniline) and as fungicides, captan plus terrachlor plus terrazole and as insecticides, disulfoton with and without phorate.
• CIPC carbamate
• DCPA terephthalate
• prometryne a triazine
• trifluralin a dinitrotoluidine
• nitralin an aniline
• Chambers et al observed significant interactions between the pesticides, with many combinations of pesticides giving a variety of negative synergistic effects, including reduction in seedling emergence, significant reduced cotton seedling survival and/or vigor and/or stand reduction and/or yield.
• C. D. Applewhite reported (Proc. SWSS, p. 83, 1990) on tests in cotton with various application modes (granular in-furrow or tank spray) of clomazone with and without fluometuron herbicides in combination with the OP insecticides disulfoton, phorate, aldecarb and acephate and the nematicide fenamiphos.
• Applewhite further reported that combinations of clomazone alone or with fluometuron applied PPI or PRE at different rates to aldecarb or phorate resulted in no adverse reactions. However, at lower rates aldecarb applied in-furrow failed to reduce cotton discoloration and stand reduction.
• herbicides which exhibit ALS inhibitory action in weed plants, especially sulfonylurea, imidazolidinones, azolopyrimidine sulfonamides, and the like.
• other herbicides not included in the foregoing classes of compounds have also exhibited negative synergy with biocides, even though such other herbicides, e.g., acetamides, thiocarbamates, etc., are not known to be ALS inhibitors, but do exhibit a similar mode of inhibitory action.
• the present invention relates to compositions comprising: (a) a herbicidal component; (b) a biocidal component and (c) an antidotal component, which latter component inhibits, reduces or prevents the tendency to interact or the actual interaction of the former two components to enhance the phytotoxicity of said herbicidal component.
• Such enhanced phytotoxicity is defined as "negative synergy or synergism”.
• this invention relates to a method for combatting, inhibiting, reducing or preventing negative synergism resulting from the interaction of herbicidal and biocidal compounds by use of an antidotal compound.
• the herbicidal component is a compound which causes an ALS inhibition reaction in plants.
• ALS inhibition is meant that the effect of the herbicide on the plant is to interrupt or inhibit the aceto lactate synthase ("ALS") enzyme in the amino acid pathway leading to plant proteins.
• ALS aceto lactate synthase
• Compounds known to exhibit such ALS inhibitory reaction in plants include sulfonylureas, imidazolinones and azolopyrimidine sulfonamides.
• herbicidal compounds which cause negative synergy, either through an ALS or non-ALS or some other form of inhibitory action in weed plants include ⁇ -haloacetamides, thiocarbamates, aliphatic and aromatic carboxylic acids, amides, salts and esters, isoxazolidinones, ureas, triazines, nitrobenzenes, etc.
• preferred herbicidal compounds useful in the present invention are selected from azolopyrimidine sulfonamide, sulfonylurea, imidazolinone, acetanilide and thiocarbamate compounds more particularly defined below.
• Preferred azolopyrimidine sulfonamide compounds useful herein include those according to Formula I or agriculturally-acceptable salts thereof: wherein
• Preferred herbicidal compounds according to Formula I are those wherein A and B are both nitrogen; R is -SO 2 N(R 6 )(R 7 ); R 1 is phenyl, pyrimidinyl, triazinyl, thiadiazolyl, pyrazinyl, pyridinyl, or any of said R 1 radicals substituted with cyano, halogen, amino, mono- or di-C 1-4 alkylamino, C 1-6 alkyl, haloalkyl, alkylthio, alkoxy, alkoxyalkyl, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl; R 2 is hydrogen, halogen, cyano, amino, mono- or di-C 1-4 alkylamino, C 1-6 alkyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkoxyalkyl, alkoxycarbonyl,
• preferred species include N-(2,6-dichloro-3-methylphenyl)-1-(4-chloro-6-methoxypyrimidinyl-2-yl)-1H-1,2,4-triazole-3-sulphonamide; N-(2,6-difluorophenyl)-1-(pyrimidin-2-yl)-5-methyl-1,2,4-triazole-3-sulphonamide; N-(2,6-dichloro-3-methylphenyl)-1-(pyrimidin-2-yl)-5-methyl-1,2,4-triazole-3-sulphonamide; N-(2-methyl-6-nitrophenyl)-1-pyrimidin-2-yl)-5-methyl-1,2,4-triazole-3-sulphonamide; N-(2,6-difluorophenyl)-1-(4,6-dimethylpyrimidin-2-yl)-5-methyl-1,2,4-triazole-3-sulphonamide; N-(2,6-difluorophenyl
• more preferred herbicidal compounds according to Formula I are those wherein A and B are both nitrogen (N), R is - SO 2 N(R 6 )(R 7 ) and R 1 and R 2 are combined to form one of the following divalent radicals:
• Preferred compounds containing the above divalent structures are those wherein R 6 is hydrogen, alkyl, alkenyl, alkoxy, alkoxycarbonyl, alkoxythiocarbonyl, alkylsulfinyl or alkylsulfonyl having up to 6 carbon atoms; amino, mono- or di-C 1-4 alkylamino or -alkylaminocarbonyl; phenyl, benzyl, benzoyl or an R 6 member when not self-inclusive substituted with one or more halogen, nitro, C 1 - 4 alkyl, haloalkyl or alkoxy radicals; R 7 is unsubstituted phenyl or pyrazolyl or optionally substituted independently with one or more phenyl, halogen, nitro, trifluoromethyl, C 1-6 alkyl, alkoxy, alkoxyalkyl, alkoxycarbonyl, -S(O) n alkyl, -S(O)
• bivalent radical (a) a compound wherein R 1 and R 2 are combined to form the bivalent radical (a) above
• its tetrahydro analogs of bivalent radical (b) or their agriculturally-acceptable salts are the following compounds:
• Representative species of the preceding compounds include the following:
• Preferred and representative herbicidal compounds according to Formula I wherein R 1 and R 2 are combined to form the bivalent radicals (c) and (d) above include tautomeric forms of the following compounds:
• Another group of preferred herbicidal compounds of Formula I are those wherein R 1 and R 2 combine to form the divalent radical (e) above, i.e., wherein
• One preferred compound according to those defined in the preceding paragraph is 5-fluoro-7-methoxy-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-c]-pyrimidine-2-sulfonamide.
• Still another group of herbicidal sulfonamide compounds useful in combination with antidotal compounds according to this invention are those identified as (6,7)-dihydro-[1,2,4]-triazolo[1,5-a]-[1,3,5]-triazine-2-sulfonamides.
• Such compounds are those according to Formula I wherein A and B are both N, R is SO 2 N(R 6 )(R 7 ) and R 1 and R 2 are combined to form divalent radical (f) above, i.e.,
• Exemplary preferred species according to the structure defined in the preceding paragraph include those wherein R 7 is phenyl substituted in the ortho positions independently with halogen, CF 3 , NO 2 , C 1-3 alkyl, alkoxy or alkoxycarbonyl and substituted in the meta and para positions with halogen, CF 3 or C 1-4 alkyl;
• Preferred species according to the preceding description include the following:
• a modification of the preceding 6,7-dihydrotriazolotriazine sulfonamides includes compounds according to Formula I wherein the only change is that B is CR 3 , rather than N; D, X, Y, R, R 6 , R 7 and R 1 combined with R 2 to form the divalent radical (f), have the same meanings as defined above and
• Preferred compounds according to this embodiment of the invention herbicides include those wherein
• Preferred species according to the preceding description include the following:
• triazolosulfonamides safened according to this invention are those according to Formula I wherein R 1 and R 2 are combined to form the divalent radical (g) above, i.e., and are characterized as thiazolotriazole sulfonamides, wherein:
• Preferred members within the above thiazolotriazole sulfonamides are those wherein X and Y are independently H or C 1-6 alkyl, preferably methyl; R 6 is H and R 7 is phenyl substituted with one or more halogen, NO 2 , C 1-4 alkyl, alkoxy, alkoxycarbonyl or alkylthio groups.
• a preferred species according to the preceding group of compounds is N-(2,6-difluorophenyl)-thiazole[3,2-b][1,2,4]triazole-2-sulfonamide.
• the first group of compounds according to this embodiment of analogous compounds described in the preceding paragraph are those wherein R 1 and R 2 are combined to form the above bivalent radical (a), i.e., or their tetrahydro analogs of bivalent radical (b) above, i.e.,
• Preferred compounds within this embodiment of herbicidal compounds are those wherein
• Preferrred species in the foregoing group of compounds include the following:
• a second group of preferred herbicides in the class of those wherein in Formula I R is N(R 4 )SO 2 R 5 includes compounds wherein R 1 and R 2 are combined to form the bivalent radical (h), i.e.,
• Exemplary compounds within this group include the following compounds wherein R 5 is a substituted phenyl radical:
• R 5 is a substituted pyrazolyl, furanyl or thiophenyl radical.
• Representative R 5 pyrazolyl members are the pyrazol-4-yl sulfonamide compounds (un)substituted in the 1-position with C 1-4 alkyl or phenyl and in the 3- and 5-positions with halogen, CN, NO 2 , CF 3 , phenyl, benzyl, C 1-4 alkyl, aminocarbonyl, mono- or dialkylamino carbonyl, alkoxycarbonyl, alkenyloxycarbonyl or alkynyloxycarbonyl, benzyloxycarbonyl or said phenyl and benzyl members substituted with halogen, C 1-4 alkyl or alkoxy.
• furanyl and thiophenyl members are the 2-yl and 3-yl isomers substituted in the substitutable positions of the 2-yl radical with one or more H, halogen or C 1-4 alkyl and in the 3-yl radical with one or more H, halogen or COO-alkyl, -alkenyl or -alkynyl having up to 6 carbon atoms. Examples of such compounds are:
• Preferred sulfonylurea compounds useful as the herbicidal component herein are those according to Formula II
• Preferred herbicidal sulfonylureas according to Formula II include:
• imidazolinones Another class of preferred compounds useful as the herbicidal component herein are the imidazolinones.
• the basic groups of relevant imidazolinones comprehended herein are (un)substituted derivatives of (4,5-dihydro-4-oxo-1H-imidazol-2-yl)benzoic acid, (4,5-dihydro-4-oxo-1H-imidazol-2-yl)nicotinic acid and (4,5-dihydro-4-oxo-1H-imidazol-2-yl)quinolinecarboxylic acid.
• Derivatives of these acids include esters, amides, salts (e.g., alkali metals, especially potassium and sodium, mono- and di-alkyl amine and ammonium salts) and homologs, isomers (positional and optical) and homologs thereof, particularly of the preferred species listed below.
• salts e.g., alkali metals, especially potassium and sodium, mono- and di-alkyl amine and ammonium salts
• homologs e.g., isomers (positional and optical) and homologs thereof, particularly of the preferred species listed below.
• Examples of important imidazolinone herbicides include:
• Another preferred class of compounds useful as the herbicidal component herein includes ⁇ -chloroacetamides according to Formula III
• Preferred herbicidal compounds according to Formula III are those wherein the R 13 member is an alkoxy- alkyl radical of the structure -(E)-O-L, wherein E and L are linear or branched-chain alkyl residues having a combined total of up to 8 carbon atoms; or a substituted or unsubstituted C 4-10 heterocyclyl or heterocyclylmethyl radical containing from 1 to 4 ring hetero atoms selected independently from N, S or O atoms and the R 14 member is also one of said heterocyclyl or heterocyclylmethyl radicals or an optionally-substituted phenyl radical.
• the phenyl radical is substituted with alkyl groups, especially in the ortho positions.
• some preferred heterocyclic members are substituted with alkyl or alkoxy radicals.
• heterocyclic R 13 and/or R 14 members of Formula III are mentioned independently, the furanyl, thienyl, pyrazolyl, pyrrolyl, isoxazolyl, isothiazolyl, triazolyl, imidazolyl, and pyrimidinyl radicals and their analogs having a methylene (-CH 2 -) moiety connecting the heterocyclic radical to the acetamide nitrogen atom, e.g., pyrazol-1-ylmethyl.
• the heterocyclic radical is attached directly to the amide nitrogen (with no intervening methylene moiety), the attachment may be through a ring carbon atom or a ring hetero atom as appropriate.
• R 13 and/or R 14 members include the following: propynyl, alkoxycarbomethyl or -ethyl, alkoxyiminoalkyl, benzyl, hydroxyalkyl, haloalkoxy and haloalkoxyalkyl, cyanoalkoxy and -alkoxyalkyl, methyl, ethyl, propyl, butyl and their isomers, and the like.
• N-(2,4-dimethylthien-3-yl)-N-(1-methoxyprop-2-yl)-2-chloroacetamide N-(1H-pyrazol-1-ylmethyl)-N-(2,4-dimethylthien-3-yl)-2-chloroacetamide and N-(1-pyrazol-1-ylmethyl)-N-(4,6-dimethoxypyrimidin-5-yl)-2-chloroacetamide.
• a larger group of preferred ⁇ -chloroacetamide and ⁇ -haloacetanilide herbicides includes the particular preferred species of Formulae III and Iv identified above.
• Yet another class of preferred compounds useful as the herbicidal component in the composition/method according to this invention are the thiocarbamates.
• a second component of the composition and method according to this invention is the biocidal compound.
• biocide(s) refers to compounds and effects thereof used to eradicate non-plant, non-vegetal pests. Examples of such pests are insects, fungicides, nematodes, mites, etc. Contemplated herein are such non-vegetal pesticides as interact with the herbicidal component in the absence of the antidotal component to effect a negative synergism between the herbicide and biocide.
• OPs organophosphates
• carbamates pyrethroids
• cyclopropanecarboxylic acids and esters carboxamides
• dicarboximides perchlorocyclohexane, etc.
• OP insecticides Because of their widespread use in agriculture, the OP insecticides have been particularly troublesome, especially when used in conjunction with sulfonylurea herbicides.
• OP insecticides examples include terbufos (active ingredient in COUNTER®), chlorpyrifos (active ingredient in LORSBAN®), disulfoton (active ingredient in DISULFOTON® and DI-SYSTON®), phorate (active ingredient in THIMET®), dimethoate (active ingredient in CYGON®), malathion (active ingredient in MALATHION), etc.
• insecticidal pesticides include, e.g., the following compounds (by common or trade name): abamectin, aldicarb, acephate, aldrin, aminocarb, azinphos, bendiocarb, carbaryl, carbofuran, fonophos, chlormephos, DDT, dicofol, diflubenzuron, endothion, fenvalerate, FORCE®, heptachlor, methiocarb, methomyl, methyl-and ethyl-parathion, permethrin, pyrethrin, terbufos, etc.
• fungicidal pesticides which may be included with the above herbicides and insecticides include the following (by common or trade name); anilazine, benodanil, benomyl, butacarb, captafol, captan, carboxin, chloranil, chlorbromuron, chloroneb, chlorthalnil, chlorquinox, dazomet, dichlofluanid, diclone, dichloroaphen, dichloran, dithianon, dodine, dinocat, edifenphos, DOWSIDE-A®, ferbam, folpet, mancozeb, maneb, pyrazophos, thiabendazole, thiram, zineb, ziram, etc.
• nematicides which may serve as a biocidal component herein include, e.g., terbufos, fensulfothion, carbofuran, ethoprop, fenamiphos, dichloropropene, aldecarb and oxamyl.
• miticides which may be used as a biocidal component of the present invention include, e.g., formetanate hydrochloride, omite, profenofos, dimethoate, DIKAR®, ethion, dinocap, dicofol, amitraz, oxythioquinox, cyhexatin, fenbutatinoxide, oxamyl and phosalone.
• the third essential component of the composition/method according to this invention is the antidotal compound.
• This compound must be present in an amount sufficient to inhibit, nullify, reduce, mitigate or prevent negative synergism from the interaction of the herbicidal and biocidal components of the invention. This is an important and distinguishing feature of the invention herein vis-a-vis prior art and, indeed, current antidote technology and practice, wherein the objective was and is to utilize the minimum amount of antidote required to safen the known or exhibited normal, inherent herbicidal property (phytotoxicity) of a given herbicide or combination of herbicides.
• the antidote technology of this invention has as its purpose the safening of enhanced herbicidal activity beyond that normally or inherently exhibited by a herbicide(s), i.e., negative synergy, generated by the interaction of a herbicide and a biocide, commonly an insecticide, especially an OP insecticide.
• a herbicide product may normally cause a commercially-unacceptable amount of injury to a crop at a given application rate in the absence of an antidote.
• crop injury at the same herbicide application rate may be readily prevented by using the necessary amount of an effective antidote.
• the critical feature of the invention is that whatever the properties of the herbicide/biocide/antidote system involved, inherent and/or environmental-use related, the amount of antidote employed will be such as to negate in part or full the negative synergy induced by the particular herbicide/biocide interaction.
• antidotal compounds encompassed herein are:
• R 17 is C 1-3 haloalkyl
• R 18 and R 19 are independently C 2-4 alkenyl or haloalkenyl or 2,3-dioxolan-2-yl-methyl and R 18 and R 19 when combined form a C 4-10 saturated or unsaturated heterocyclic ring containing O, S and/or N atoms and which may be substituted with C 1-5 alkyl, haloalkyl, alkoxy, or alkoxyalkyl or haloacyl groups.
• the preferred haloalkyl R 17 member in Formula V is dichloromethyl.
• Preferred species in this group of antidotal compounds are N,N-diallyl-dichloroacetamide and N-(2-propenyl)-N-(1,3-dioxolanylmethyl)dichloroacetamide (Code No. PPG-1292).
• Still more preferred antidotal compounds according to Formula V is a sub-group of substituted 1,3-oxazolidinyl dichloroacetamide having the formula wherein
• Preferred members according to Formula VI are those wherein R 20 is hydrogen or one of said heterocyclylmethyl members and R 21 and R 22 are independently methyl, trifluoromethyl or when combined with the carbon atom to which attached form a C 5 or C 6 cycloalkyl radical.
• Preferred antidotal compounds according to Formula VI are the following compounds:
• dichloroacetamide antidotal compounds are the following compounds:
• Still another preferred group of antidotal compounds are the following which have a structure not according to Formula V, i.e., those in Paragraph (b) above:
• herbicidal and antidotal compounds of Formulae I-VI are known in the art.
• compositions of particular and preferred interest herein include combinations of the herbicidal components: nicosulfuron, primisulfuron, DPX-E9636, NC-311, NC-319 acetochlor and XRD-498 (N-(2,6-difluorophenyl)-5-methyl(1,2,4)-triazolo[1,5-a]pyrimidine-2-sulfonamide); the biocidal components terbufos, chlorpyrifos, disulfoton and phorate and the antidotal components: dichlormid (R-25788), PPG-1292 (N-(2-propenyl)-N-(1,3-dioxolan-2-ylmethyl)dichloroacetamide), AD-67 and MON-13900 (oxazolidine, 3-(dichloroacetyl)-2,2-dimethyl-5-(2-furanyl)-) and other compounds according to Formulae V and VI.
• the herbicidal components nicosul
• compositions comprised of nicosulfuron, primisulfuron, DPX-E9636, NC-311, NC-319 or acetochlor as the herbicidal component; phorate, terbufos or chlorpyrifos as the insecticidal component and AD-67 or MON-13900 as the antidotal component.
• the components of the composition may comprise individual members of each class, i.e., herbicidal, biocidal and antidotal components, or combinations of members of each class, particularly the herbicidal and biocidal classes.
• herbicidal compounds which may be particularly suitable as co-herbicides with the preferred ALS inhibitor classes of herbicides, i.e., sulfonylureas, imidazolinones and azolopyrimidine sulfonamides, are further exemplified below.
• compositions of this invention are not limited to those the herbicidal component of which operates via the ALS inhibition or similar mode of action in a weed plant. More broadly this invention contemplates the inhibition or reduction of negative synergy arising from any combination of herbicidal and biocidal components, regardless of the mode of action in the plant's system, by means of a sufficient quantity of antidotal compound to effect weed control and crop safety.
• compositions may be formed in a variety of ways, including tank mixing the said separate components for either bulk dispersal or for pre-packaging for storage, transportation, sale and use. Said compositions are also formed when the individual components are separately applied to the locus of use and there combine in contact with each other simultaneously or sequentially in any order.
• the biocidal components may be first applied to the soil alone or together with the antidotal component, followed by application of the herbicidal component or the antidotal component may be applied to the seeds of the crop plant prior to planting in soil previously or subsequently treated with the biocidal component.
• the only caveat in forming said composition is that the antidotal component always be present to combat negative synergy.
• haloalkyl embraces radicals wherein any one or more of the carbon atoms, preferably from 1 to 4 in number, is substituted with one or more halo groups, preferably selected from bromo, chloro and fluoro.
• haloalkyl preferably selected from bromo, chloro and fluoro.
• monohaloalkyl, dihaloalkyl and polyhaloalkyl groups may have either a bromo, a chloro, or a fluoro atom within the group.
• Dihaloalkyl and polyhaloalkyl groups may be substituted with two or more of the same halo groups, or may have a combination of different halo groups.
• a dihaloalkyl group may have two bromo atoms, such as a dibromomethyl group, or two chloro atoms, such as a dichloromethyl group, or one bromo atom and one chloro atom, such as a bromochloromethyl group.
• Examples of a polyhaloalkyl are perhaloalkyl groups such as trifluoromethyl and perfluoroethyl groups.
• halogen attached to the acetyl radical is the chlorine ion
• the other halogens i.e., bromo, iodo or fluoro may be substituted for the chloro.
• Preferred haloalkyl R 17 members of Formula V are dihalomethyl, particularly dichloromethyl, while the preferred haloalkyl R 18 member is a tri-halogenated methyl radical, preferably trifluoromethyl.
• alkyl is used either alone or in compound form (as in “haloalkyl”), it is intended to embrace linear or branched radicals having up to four carbon atoms, the preferred members being methyl and ethyl.
• agriculturally-acceptable salts of the compounds defined by the above formula is meant a salt or salts which readily ionize in aqueous media to form a cation or anion of said compounds and the corresponding salt anion or cation, which salts have no deleterious effect on the antidotal properties of said compounds or of the herbicidal properties of a given herbicide and which permit formulation of the herbicide-antidote composition without undue problems of mixing, suspension, stability, applicator equipment use, packaging, etc.
• antidotally-effective is meant the amount of antidote required to reduce the phytotoxicity level or effect of a herbicide, preferably by at least 10% or 15%, but naturally the greater the reduction in herbicidal injury the better.
• herbicide-effective is meant the amount of the herbicide component (individual or plural) required to effect a meaningful injury or destruction to a significant portion of affected undesirable plants or weeds. Although of no hard and fast rule, it is desirable from a commercial viewpoint that 80-85% or more of the weeds be destroyed, although commercially significant suppression of weed growth can occur at much lower levels, particularly with some very noxious, herbicide-resistant plants.
• antidote "safening agent”, “safener”, “antagonistic agent”, “interferant”, “crop protectant” and “crop protective” are often-used terms denoting a compound capable of reducing the phytotoxicity of a herbicide to a crop plant or crop seed.
• crop protectant and “crop protective” are sometimes used to denote a composition containing as the active ingredients, a herbicide-antidote combination which provides protection from competitive weed growth by reducing herbicidal injury to a valuable crop plant while at the same time controlling or suppressing weed growth occurring in the presence of the crop plant.
• Antidotes protect crop plants by interfering with the herbicidal action of a herbicide on the crop plants so as to render the herbicide selective to weed plants emerging or growing in the presence of crop plants.
• Herbicides which may be used as co-herbicides with the azolopyrimidine sulfonamides of Formula I, the sulfonylureas of Formula II, ⁇ -haloacetamides of Formulae III or IV, the imidazolinones and thiocarbamate components of the invention composition and method with benefit in combination with an antidotes as described herein include, heterocyclyl phenyl ethers (especially phenoxypyrazoles) and pyridines and many others.
• herbicides e.g., triazines, ureas, diphenyl ethers, benzoic acid derivatives, nitroanilines, thiazoles, isoxazoles, pyrrolidinones, aromatic and heterocyclic di- and triketones, etc.
• the individual members of which classes may be derivatives having one or more substituents selected from a wide variety of radicals may suitably be used as co-herbicides.
• Such combinations can be used to obtain selective weed control with low crop injury in several varieties of monocotyledonous crop plants such as corn, grain sorghum (milo), and cereals such as wheat, rice, barley, oats, and rye, as well as several varieties of dicotyledonous crop plants including oil-seed crops such as soybeans and cotton.
• monocotyledonous crop plants such as corn, grain sorghum (milo)
• cereals such as wheat, rice, barley, oats, and rye
• dicotyledonous crop plants including oil-seed crops such as soybeans and cotton.
• Particular utility for the antidotal compounds of this invention has been experienced with various herbicides in corn, sorghum and soybeans.
• pyridine herbicides examples include:
• Examples of important benzoic acid derivative herbicides include:
• the herbicides of particular and preferred interest as co-herbicides with the azolopyrimidine sulfonamides, imidazolinones and sulfonylurea in compositions with antidotes according to this invention include each of the above-mentioned species from different chemical classes of compounds exemplified as important herbicides, particularly those of current commercial interest and use and those which may be determined of commercial utility.
• Co-herbicidal compounds of preference include the following:
• composition containing the herbicide/biocide/antidote combination may also contain other additaments, e.g., fertilizers, inert formulation aids, e.g., surfactants, emulsifiers, defoamers, dyes, extenders, etc.
• fertilizers e.g., fertilizers, inert formulation aids, e.g., surfactants, emulsifiers, defoamers, dyes, extenders, etc.
• inert formulation aids e.g., surfactants, emulsifiers, defoamers, dyes, extenders, etc.
• herbicides have varying degrees of phytotoxicity to various plants because of the sensitivity of the plant to the herbicide.
• certain crops such as corn and soybeans have a high level of tolerance (i.e., low sensitivity) to the phytotoxic effect of alachlor
• other crops e.g., milo (grain sorghum), rice and wheat
• have a low level of tolerance i.e., high sensitivity
• the same type of sensitivity to herbicides as shown by crop plants is also exhibited by weeds, some of which are very sensitive, others very resistant to the phytotoxic effects of the herbicide.
• the "selectivity factor" of the herbicide for preferentially injuring the weed while not injuring the crop is high.
• an antidotal compound may, and commonly does, have varying degrees of crop protective effect against different herbicides in different crops. Accordingly, as will be appreciated by those skilled in the art, the various antidotes of this invention, as with all classes of antidotal compounds, will have greater or lesser crop safening effects against various herbicides and herbicide combinations in various crops than in others.
• a given antidotal compound may have no crop protective ability against a given herbicide in a given crop
• that same antidotal compound may have a very high crop protective ability against the same given herbicide in a different crop or against a different herbicide in the same crop at the same or different rate of application or in a different application mode, i.e., PPI, PRE, seed dressing, etc.. This is an expected phenomenon.
• Effective weed and non-plant pest control coupled with low crop injury is a result of treatment of a plant locus with a combination of herbicide, biocide, e.g., insecticide compounds and antidote compounds.
• plant locus application to the "plant locus” is meant application to the plant growing medium, such as soil, as well as to the seeds, emerging seedlings, roots, stems, leaves, or other plant parts.
• the phrase "combination of herbicide and/or insecticide compound and antidote compound” embraces various methods of treatment.
• the soil of a plant locus may be treated with a "tank-mix" composition containing a mixture of the herbicide, insecticide and the antidote which is "in combination”.
• the soil may be treated with the herbicide, insecticide and antidote compounds separately so that the "combination" is made on, or in, the soil.
• the herbicide, insecticide and antidote may be mixed into or incorporated into the soil either by mechanical mixing of the soil with implements or by "watering in” by rainfall or irrigation.
• the soil of a plant locus may also be treated with antidote by application of the antidote in a dispersible-concentrate form such as a granule.
• the granule may be applied to a furrow which is prepared for receipt of the crop seed and the herbicide and insecticide may be applied to the plant locus either before or after in-furrow placement of the antidote-containing granule so that the herbicide, insecticide and antidote form a "combination".
• Crop seed may be treated or coated with the antidote compound either while the crop seed is in-furrow just after seeding or, more commonly, the crop seed may be treated or coated with antidote prior to seeding into a furrow.
• the herbicide and insecticide may be applied to the soil plant locus before or after seeding and a "combination" is made when both herbicide, insecticide and antidote-coated seed are in the soil.
• herbicide, insecticide and antidote are also contemplated as a "combination" in a commercially-convenient association or presentation of herbicide, insecticide and antidote.
• the herbicide, insecticide and antidote components in concentrated form may be contained in separate containers, but such containers may be presented for sale or sold together as a "combination” (composition).
• the herbicide, insecticide and antidote components in concentrated form may be in a mixture in a single container as a "combination”. Either such "combination” may be diluted or mixed with adjuvants suitable for soil applications.
• Another example of a commercially-presented combination is a container of antidote-coated crop seed sold, or presented for sale, along with a container of herbicide or insecticide material.
• These containers may, or may not, be physically attached to each other, but nonetheless constitute a "combination of herbicide, insecticide and antidote" when intended for use ultimately in the same plant locus.
• the amount of antidote employed in the methods and compositions of the invention will vary depending upon the particular herbicide and herbicide/insecticide combination with which the antidote is employed, the rate of application of the herbicide, the particular crop to be protected, and the manner of application to the plant locus.
• the amount of antidote employed is a safening-effective amount, that is, the amount which reduces, or protects against, crop injury and negative synergism that otherwise would result from the presence of the herbicide and insecticide.
• the amount of antidote employed will be less than an amount that will substantially injure the crop plant.
• the antidote can be applied to the crop plant locus in a mixture with the selected herbicide and/or insecticide.
• a suitable mixture of antidote and herbicide and/or insecticide whether in a homogeneous liquid, emulsion, suspension or solid form, can be applied to the surface of, or incorporated in, the soil in which the seed has been planted.
• the herbicide/insecticide/antidote mixture may be applied to the soil, and then the seed thereafter "drilled” into the soil below the soil layer containing the herbicide/insecticide/antidote mixture.
• the herbicide will reduce or eliminate the presence of undesirable weed plants.
• the presence of the antidote will reduce or eliminate the injury to the crop seed caused by the herbicide often exacerbated by an insecticide. It is not essential that the application of herbicide, insecticide and the antidote to the plant locus be made using the selected herbicide, insecticide and antidote in the form of a mixture or composition.
• the herbicide and the antidote or the insecticide and antidote may be applied to the plant locus in a sequential manner.
• the insecticide and/or antidote may be first applied to the plant locus and thereafter the herbicide is applied.
• the herbicide may be first applied to the plant locus and thereafter the antidote with or preceding application of the insecticide is applied.
• the ratio of herbicide to antidote may vary depending upon the crop to be protected, weed to be inhibited, herbicide used, etc., but normally a herbicide-to-antidote ratio ranging from 1:25-to-60:1 (preferably 1:5-to-30:1) parts by weight may be employed, although much higher rates of antidote may be used, e.g., 1:100-1:300 parts by weight of herbicide-to-antidote.
• the antidote may be applied to the plant locus in a mixture, i.e., a mixture of a herbicidally-effective amount of herbicide and a safening-effective amount of an antidote, or sequentially, i.e., the plant locus may be treated with an effective amount of the herbicide followed by a treatment with the antidote or vice versa.
• effective herbicidal amounts are in the range of about 0.03 to about 12 kilograms/hectare, but rates as low as 0.004 kg/ha may be used effectively.
• the preferred range of rate of application is from about 0.1 to about 10 kg/ha.
• antidote application rates range from about 8-10 kg/ha down to about 0.05 kg/ha. It will be appreciated that at times amounts either below or above these ranges will be necessary to obtain the best results.
• the selection of the herbicide to inhibit the emergence and growth of weeds depends upon the species of weeds to be controlled and the crop to be protected.
• the biocide will be applied at rates recommended by the supplier/manufacturer.
• the application of the antidote can be made directly to the seed before planting.
• a quantity of crop seed is first coated with the antidote.
• the coated seed is thereafter planted.
• the herbicide may be applied to the soil before or after the coated seed is planted.
• the herbicide, insecticide, antidote, or a mixture thereof may be applied to the plant locus without any adjuvants other than a solvent.
• the herbicide, insecticide, antidote, or a mixture thereof is applied in conjunction with one or more adjuvants in liquid or solid form.
• Compositions or formulations containing mixtures of an appropriate herbicide, insecticide and antidote usually are prepared by admixing the herbicide, insecticide and antidote with one or more adjuvants such as diluents, solvents, extenders, carriers, conditioning agents, water, wetting agents, dispersing agents, or emulsifying agents, or any suitable combination of these adjuvants.
• These mixtures may be in the form of particulate solids, granules, pellets, wettable powders, dusts, solutions, aqueous dispersions, or emulsions.
• herbicide, insecticide, antidote, or mixture thereof can be carried out by conventional techniques utilizing, for example, hand-carried or tractor-mounted spreaders, power dusters, boom and hand sprayers, spray dusters, and granular applicators. If desired, application of the compositions of the invention to plants can be accomplished by incorporating the compositions in the soil or other media.
• the insecticide may be applied to the soil followed by application of the antidote alone or in admixture with the herbicide.
• Various sequential modifications of application of the chemicals is contemplated.
• the herbicide, biocide and/or antidote may be applied preemergence by preplant incorporation surface application or postemergence. The only condition being that the insecticide and herbicide not be active in the plant in the absence of the antidote in order to prevent or reduce negative synergism induced by interaction of the herbicide and insecticide.
• Biocide No. Nomenclature 1 S-[[(1,1-dimethyl-ethyl)thio]-methyl]O,O-diethylphosphorodithioate; (common name "terbufos", active ingredient in COUNTER®) 2 O,O-Diethyl O-(3,5,6-trichloro-2-pyridyl)phosphorothioate; (common name "chlorpyrifos", active ingredient in LORSBAN®); 3 2,3,5,6-tetrafluoro-4-methylbenzyl-(Z(-(1 RS, 3RS)-3-(2-Chloro-3,3,3-trifluoroprop-1-ethyl)-2, 2-dimethyl-cyclopropane carboxylate (common name "tefluthin”, active ingredient in FORCE®); 4 2,3-Dihydro-2,2-dimethyl-7-benz
• Herbicide No. Nomenclature 1 N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-chloro-4-methoxycarbonyl-5-sulfonamide; (Code No.
• EPTC Co-Herbicide D herein
• ERADICANE is a well-known herbicide by itself or as a mixture with an antidote, dichlormid, (ERADICANE®) or in combination with another antidote, R-29148, and a soil-life extender, dietholate, (ERADICANE® EXTRA).
• ERADICANE is used as the herbicide/antidote composition
• the biocidal component is an organophosphorus compound other than fonofos.
• Containers were filled and compacted with a fumigated silt loam top soil to a depth of about 1.3 cm from the top of the container.
• a first container was designated as an untreated control
• a second container was designated as a herbicide control
• a third container was designated as a herbicide + antidote test container.
• Each of the containers was seeded with a crop species.
• a measured amount of herbicide dispersed or dissolved in acetone was applied to a measured quantity of soil.
• To this same quantity of soil treated with herbicide there was added a measured amount of antidote dispersed or dissolved in acetone.
• the quantity of soil treated with the herbicide and antidote was thoroughly mixed to incorporate the herbicide and antidote in the soil uniformly.
• the seed bed in the third container of soil was covered with the soil treated with the herbicide and antidote and the container was leveled.
• the seed beds of the first and second containers were likewise covered by soil layers.
• the cover layer of the first container was not treated with herbicide or antidote.
• the cover layer of the second container had a measured quantity of herbicide alone incorporated therein.
• Insecticide application was made as described in the tests in the examples below.
• the containers were then placed on a bench in a greenhouse and sub-irrigated as required for the duration of the test. Plant response was observed at various times, but usually about three weeks after initial treatment; variations will be noted in the examples.
• Procedure II This procedure is the same as Procedure I, but modified in the manner that after incorporation of the chemicals (herbicide, antidote and insecticide), the containers with the covered seedbed were treated with an initial overhead irrigation equivalent to 0.6 cm rainfall, then subsequently sub-irrigated as required on greenhouse benches.
• the chemicals herebicide, antidote and insecticide
• the following procedure shows interaction between a herbicide and antidote when the antidote is applied in a soil furrow containing crop seed and the herbicide is incorporated in a soil cover layer.
• Containers were filled and compacted with fumigated silt loam soil to a depth of about 1.3 cm from the top of the container.
• a first container was designated as an untreated control
• a second container was designated as a herbicide control
• a third container was designated as a herbicide + antidote test container.
• Each container was seeded with crop seed in marked furrows.
• Antidote compound, dissolved in acetone was applied directly to the seeded furrows of the third container.
• Antidote application rate was 0.55 mg active compound per inch of furrow (0.22 mg/cm). This rate was comparable to a plot application rate of 0.28 kilogram per hectare (kg/ha), based on 76 cm (30") spaced-apart furrows.
• each of the second and third containers was filled and leveled with a cover layer of soil having incorporated therein the selected herbicide at a predetermined concentration.
• the first container was filled and leveled with soil containing no herbicide.
• Insecticides were applied in the manner described in the examples below. Pots were overhead irrigated with 0.6 cm (1/4"), then placed on a bench in a greenhouse and sub-irrigated as required for the duration of the test. Plant response was observed about three weeks after initial treatment, unless otherwise indicated.
• Containers were filled and compacted with a steam sterilized silt loam soil to a depth of about 1.3 cm from the top of the container.
• a first container was designated as an untreated control
• a second container was designated as a herbicide control
• a third container was designated as a biocide control
• a fourth container as a herbicide + biocide control
• a fifth container as a herbicide + biocide + antidote test container.
• Each of the containers was seeded with a crop species and weed species.
• a measured amount of herbicide dispersed or dissolved in acetone was applied to a measured quantity of soil.
• the quantity of soil treated with the herbicide was thoroughly mixed to incorporate the herbicide.
• a sample of this soil was taken and used to cover the seed bed of the second container.
• a measured amount of the biocide formulated as granules or an acetone slurry of granules was applied to the soil previously treated with herbicide and this soil was thoroughly mixed to incorporate the biocide.
• a sample of this soil was taken and used to cover the seed bed of the fourth container.
• a sample of the remaining soil was taken and a measured amount of antidote dissolved or dispersed in acetone was applied to the soil previously treated with the herbicide and biocide and this soil was thoroughly mixed to incorporate the antidote.
• This sample of soil was used to cover the seed bed of the fifth container.
• the seed beds of the first and third containers were likewise covered by soil layers.
• the cover layer of the first container was not treated with herbicide, biocide or antidote.
• the cover layer of the third container had a measured quantity of biocide alone incorporated therein.
• This procedure describes interaction among herbicide, biocide and antidote when the biocide and antidote are incorporated in a soil cover layer before emergence of crop and weed species and the herbicide subsequently applied after emergence of the crop and weeds.
• the soil, planting method and containers were described in Procedure IV.
• a measured amount of the biocide formulated as granules or an acetone slurry of granules was applied to a measured quantity of soil.
• the quantity of soil treated with the biocide was thoroughly mixed to incorporate the biocide. Samples of soil were withdrawn and used to cover the seed beds of the third (biocide control) and fourth (herbicide + biocide control) containers.
• a sample of the remaining soil was taken and a measured amount of antidote dissolved or dispersed in acetone was applied to the soil previously treated with the biocide and the soil was thoroughly mixed to incorporate the antidote.
• This sample of soil was used to cover the seed bed of the fifth container (herbicide + biocide + antidote).
• the seed beds of the first container (untreated control) and second container (herbicide control) were likewise covered by soil layers not treated with biocide or antidote.
• the containers were then placed on a bench in a greenhouse and subirrigated as required for the duration of the test.
• the herbicide dispersed in water containing 0.25% nonionic surfactant (e.g., X-77) was applied by a track sprayer at a rate of approximately 187 L/ha to the emerged plants of the second, third and fourth containers about five days after planting ("DAP" in tables below). All treatments were run in duplicate. Plant response was observed according to Procedure V. Variations in this procedure will be noted in the examples.
• nonionic surfactant e.g., X-77
• This procedure describes interaction among herbicide, biocide and antidote when the herbicide is incorporated in a soil cover layer and the biocide and the antidote are applied in a soil furrow containing crop seed before emergence of the crop.
• the soil and seeding depth were described in Procedure IV.
• a first container was designated as an untreated control
• a second container was designated as a herbicide control
• a third container was designated as a herbicide + biocide control
• a fourth container as a herbicide + biocide + antidote test container.
• the biocide and antidote were formulated as granules.
• the biocide was applied to the soil furrows of the third and fourth containers at an application rate of 1.1 mg of active compound per cm of row.
• the antidote was applied to the soil furrow of the fourth container at an application rate of 0.37 mg of active compound per cm of row.
• a measured amount of the herbicide dispersed or dissolved in acetone was applied to a measured quantity of soil.
• the quantity of soil treated with the herbicide was thoroughly mixed to incorporate the herbicide. Samples of this soil were used to cover the seed beds of the second, third and fourth containers. For each test series, the seed bed of the first container was likewise covered by a soil layer not treated with herbicide and without biocide or antidote in the soil furrow.
• This procedure describes interaction among herbicide, biocide and antidote when the biocide and the antidote is applied to a soil furrow containing crop seed before emergence of the crop and the herbicide is applied after emergence of the crop and weeds.
• the soil and planting depth was described in Procedure IV.
• the containers for comparison, the biocide and antidote applications to soil furrows were described in Procedure VI.
• the seed beds of the first, second, third and fourth containers are covered by soil layers not treated with herbicide. The containers were then placed on a bench in a greenhouse and subirrigated as required for the duration of the test.
• This procedure describes interaction among herbicide, biocide and antidote when the biocide is applied to a soil furrow containing crop seed before emergence of the crop and the herbicide and antidote are applied after emergence of the crop and weeds.
• the soil and seeding depth was described in Procedure IV.
• a first container was designated as an untreated control
• a second container was designated as a herbicide control
• a third container was designated as a biocide control
• a fourth container as herbicide + biocide control
• a fifth container as a herbicide + biocide + antidote container.
• the biocide was formulated as a granule.
• the biocide was applied to the soil furrows of the third, fourth and fifth containers at an application rate of 1.1 mg of active compound per cm of row.
• the seed beds of the first through fifth containers were covered by a soil layer of untreated soil.
• the containers were then placed on a bench in a greenhouse and subirrigated as required for the duration of the test.
• the antidote, formulated in acetone:water (1:1) containing 0.25% v/v nonionic surfactant (X-77) was applied to the emerged plants of container five by a track sprayer (187 L/ha). Likewise the emerged plants of the second and third containers were sprayed with acetone:water (1:1) containing 0.25% nonionic surfactant (X-77).
• Biocide is used in a generic sense to embrace the various utilities, a product is known to have, i.e., as an insecticide, fungicide, nematicide, miticide, etc.
• the compounds terbufos and ethoprop havecommercial utility both as an insecticide and as a nematicide.
• dimethoate has utility both as a miticide and as an insecticide.
• the particular utility of the compound is of no relevance to the invention herein, which is directed to the prevention, reduction or mitigation of the hyperphytotoxicity (negative synergism) frequently induced in plants by the interaction of a herbicidal compound and a biocidal compound, whatever its intended utility.
• test plants have the following abbreviations:
• This example was designed to investigate the degree of corn injury by Herbicide No. 1 in contact with Insecticide Nos. 1 and 2 with and without the presence of Antidote No. 1.
• VELE The weed velvetleaf (Abutilon theophrasti) used in this and subsequent tests is abbreviated as "VELE".
• Insecticide No. 1 was suspended in water as the carrier, and pipetted in-furrow over corn seeds.
• a 3.36 kg/ha emulsified concentration (EC) of Insecticide No. 2 was applied by broadcasting over cover layers via track sprayer.
• Formulations of Herbicides No. 2 and 9 were applied via track sprayer; technical grade Herbicide No. 1 and Antidote No. 1 were applied by pipet.
• the cover layer treatments were applied sequentially and incorporated over the seed beds. Overhead irrigation was applied at a rate of 0.6 cm. Observations were made three (3) weeks after treatment. Results are shown in Table 2.
• Insecticide Nos. 3 and 4 were formulated in water at a rate of 2.0 ml/75 mg and pipetted in-furrow over the seeds as in Procedure III.
• Technical grade Herbicide No. 1 and Antidote No. 1 were dissolved in acetone and sequentially pipetted onto cover layers and Herbicide No. 2 in water as an EC was applied via track sprayer.
• the herbicides and antidote were incorporated into the soil and spread over the insecticide-treated seedbeds. Overhead irrigation was immediately provided to give 0.6 cm simulated rainfall. Observations of plant injury were made three (3) weeks later. Results are shown in Table 3.
• This example illustrates the interaction between the Insecticide No. 2 (chlorpyrifos) and three sulfonylureas, Herbicide No. 4 (DPX-M6316), No. 5 (chlorimuron ethyl), No. 1 (NC-319) and an imidazolinone compound. Herbicide No. 6 (imazethapyr). Again, Antidote No. 1 was used to evaluate its effect on any negative synergy induced by interaction of herbicide and insecticide.
• Example 6 Other greenhouse tests were conducted involving the same chemicals and procedures used in Example 6, to determine any effects from microbial breakdown relative to interactions between the herbicide and insecticides in sterile vs. unsterile soils. It was found that interactions from Insecticide Nos. 1 and 2 did not appear to be reduced in unsterile vs. sterile soil, indicating little insecticide breakdown due to microbes. However, herbicide injury in general was slightly decreased in unsterile soil. This finding comports with reports in the trade that organophosphates are known to suffer microbial breakdown due to soil microbes.
• test chemicals were applied in various modes including pre-plant incorporated (PPI), post emergence (POE) and preemergence (PRE) with and without a safener (antidote).
• Test Chemicals were Herbicide Nos 1, 2, 3 and 7-9; Insecticide No. 1 and Antidote No. 1.
• Insecticide No. 1 was T-banded or furrow applied at labeled rates prior to planting corn.
• PPI herbicide treatments were applied prior to insecticide applications; PRE treatments were applied after the insecticide application either prior to or after seeding the corn.
• POE herbicide applications were made at 2 corn-growth stages, i.e., early post (EP) at the 2-3 leaf stage and late post (LP) at the 4-7 leaf stage. Plots were small plot with 3 replications in a randomized complete block design.
• EP early post
• LP late post
• Antidote No. 1 was applied as a tankmix in both treatments.
• that antidote was applied as a tank mix with the herbicide at the EP and LP stages.
• Insecticide No. 1 increased herbicidal injury to corn from combinations of Herbicide No. 1 with Herbicide Nos. 2, 3 and from combinations of Herbicide Nos. 2 and 9. Increased injury expressed itself in terms of malformed plants, stand reduction and growth reduction.
• Herbicide No. 1:Antidote No. 1 and at a 30:1 ratio of Herbicide No. 2:Antidote No. 1 crop injury was reduced from non-commercially-acceptable to commercially-acceptable levels in both PRE and PPI applications.
• Higher antidote rates of 1:3 (herbicide:antidote) improved corn tolerance even further.
• Antidote No. 1 provided safening of all crop injury expressions.
• Antidote No. 1 applied as a tankmix in POE applications, effectively safened insecticide interactions with POE applications of Herbicide No. 7.
• the above field trials demonstrated significant negative synergy induced in representative sulfonylurea herbicides with a representative organophosphate insecticide.
• Antidote No. 1 a representative dichloroacetamide antidote, provides effective safening of that negative synergism from POE, PRE and PPI herbicide applications.
• Antidote No. 1 also effective safened negative synergism in PRE and PPI applications of Herbicide No. 2 (acetochlor) and the OP insecticide.
• the corn injury/safening described in these field trials refers to commercially-unacceptable to commercial-acceptable performance.
• the criteria for commercially-acceptable corn injury is equal to or less than about 10% malformed plants or stand reduction and no greater than about 15% growth reduction.
• Examples 8-20 describe preplant incorporation of the antidote and biocide followed by postemergence application of the herbicide according to Procedure V.
• Example 10 The test conducted in this example was similar to that conducted in Example 10, including the dates of application of chemicals and taking observations. The sole difference was that thimet was used instead of chlorpyrifos and the herbicide rate was increased to 0.14 kg/ha. Thimet® 10G (also known as "phorate") is Biocide No. 10 in the above list of biocides. Test results are shown in Table 10. Herb. No. 8 (Kg/Ha) Biocide No. 10 (Kg/Ha) Antidote No.
• the biocide was No. 1 (COUNTER 15G).
• the herbicide was applied POE at the above-mentioned leaf-stage of growth of the plants five (5) days after planting the seed and observations were made eight (8) days later, i.e., thirteen (13) days after planting. Test results are shown in Table 11.
• Example 12 The same procedure described for Example 12 was conducted using the same herbicide and antidotes but using 0.56 kg/ha of ACCENT herbicide and a different biocide, viz. Biocide No. 9 (DYFONATE 10G). Chemicals were applied as in Example 12. Test data are reported in Table 12. Herbicide No. 7 (Kg/Ha) Biocide No. 9 (Kg/Ha) Antidote No.
• Example 14 Another test conducted as in Example 14 was repeated but modified only to use Biocide No. 10 (THIMET 20G) and increase the herbicide rate to 0.84 kg/ha. Test results are shown in Table 14. Herbicide No. 7 (Kg/Ha) Biocide No. 2 (Kg/Ha) Antidote No.
• biocide was DYFONATE 10G. All other test conditions were the same as in Example 16. Test results are shown in Table 16. Herbicide No. 18 (Kg/Ha) Biocide No. 9 (Kg/Ha) Antidote No.
• Example 18 The identical procedure described in Example 18 was conducted, except for use of the insecticide THIMET 20G (Antidote No. 10) here. Results are shown in Table 18.
• Herbicide No. 18 Kg/Ha
• Biocide No. 10 Kg/Ha
• Control of the weeds was generally at expected levels for safened combinations of antidotes with PURSUIT.
• the herbicide application mode was postemergence according to Procedure V.
• Other sets of tests were conducted using the PPI method of herbicide application according to Procedure IV described above.
• Herbicide Nos. 1 NC-319; also, MON-12000
• 21 XRD-4908
• the only procedural difference in these examples is the dates on which the tests were initiated and plant response observations were made; intervals between those events were the same (11 or 12 days).
• the herbicide application rate was 0.14 kg/ha; the biocide rate was 8.96 kg/ha and the antidote rate was 4.48 kg/ha or 8.96 kg/ha.
• test reported in this example was a duplicate of that in the preceding example, but for substitution of DYFONATE 10G as the biocidal component.
• the test data for this example is shown in Table 20.
• test reported in this example was a duplicate of that in the preceding example, but for substitution of DYFONATE 10G as the biocidal component.
• the test data for this example is shown in Table 24.
• the experiment conducted in this example was designed to compare the relative antidotal efficacy of Antidote No. 12 (MON-7400) and No. 1 (MON-13900) with that of a commercial safener, i.e., CGA-154281 (Antidote No. 28) against negative synergy induced by the interaction of COUNTER 15G (Biocide No. 1) with Herbicide No. 1 (MON-12000) and No. 21 (XRD-498) in corn.
• the test here was conducted according to Procedure IV, wherein herbicides and biocides and antidotes interact under PPI conditions. Observations made 13 days after planting. Test data are shown in Table 27. Herb. No.
• This example had as its objective the same comparative antidotal efficacy evaluation as in Example 28, except with different herbicides, viz. BEACON, ACCENT and PURSUIT (Herb. Nos. 8, 7 and 18, respectively). Also, these tests were conducted according to the Procedure V described above, wherein the herbicides were applied POE five (5) DAP (PPI) of COUNTER 15 G; observations were taken thirteen (13) DAP. Test data are shown in Table 28. Herbicide No. COUNTER® 15G (Kg/Ha) Antidote No.
• Antidote No. 28, (CGA-151281), was comparable to MON-13900 (No. 1), but less effective than MON-7400 for safening negative synergy generated by combinations of COUNTER with BEACON and ACCENT. Both MON-7400 and MON-13900 were more active than Antidote No. 28 in relieving corn injury from COUNTER/PURSUIT negative synergy.
• XRD-498 was applied PPI in accordance with Procedure IV above.
• the herbicides were applied thirteen (13) days initiation of the PPI operation of seed and insecticide. Observations of plant response were made nine (9) days later. Timing of observation dates were slightly different in the PPI tests.
• BEACON was applied POE five (5) days after the PPI application of COUNTER insecticide according to Procedure V. Test plants were corn and the weeds shattercane and velvet leaf. Plant response observations were made nine (9) days later. Results of this test are shown in Table 29.
• Example 36 The identical procedure in Example 36 was conducted simultaneously with this test, except for use of the herbicide PURSUIT here. Results are shown in Table 36.
• PURSUIT® Kg/Ha
• COUNTER® 15G Kg/Ha
• Tables 29-37 show that corn injury was increased from 0-5% to 55-70% when COUNTER was used in conjunction with BEACON, PURSUIT or XRD-498.
• the dichloroacetamide antidotes tested in Examples 3-37 were more effective in BEACON than with PURSUIT and XRD-498.
• MON-13900 was the most active antidote in these tests followed by Antidote Nos. 27 and 34.
• nineteen of twenty of the tested dichloroamide antidotes exhibited significant safening activity, again, led by MON-13900.
• Significant activity was also shown by seventeen of twenty benzhydryl-class antidotes, of which Antidote No.
• Herbicide Nos. 5 (chlorimuron ethyl, active ingredient in CLASSIC® herbicide), 7 (nicosulfuron, active ingredient in ACCENT® herbicide) and 15 (tribenuron methyl, active ingredient in EXPRESS® herbicide) were substituted as test herbicides. Test results are shown in Table 39.
• This example was designed to test the safening effect of those above safeners used in this test series to relieve corn injury by negative synergism induced by interaction of COUNTER 15G and three imidazolinone herbicides, i.e., imazaquin and imazapyr (used in the POE tests in Example 41) and AC 263222 (a.i. in CADRE® herbicide).
• this test was a PPI test according to Procedure VI described above. Observation of test results (Table 43) were taken thirteen 913) days after in-furrow PPI preparation.
• test antidotes exhibited varying degrees of safening the corn from the enhanced phytotoxicity due to the interaction of COUNTER 15G with the imidazolinone herbicides. Optimization of test conditions for maximum protection was not undertaken in this or any other tests described herein.
• Another test of this invention involved the safening effects of the safeners in this series against negative synergy inducted by the interaction of COUNTER 15G and a sulfonylurea herbicide (OUST®), Herbicide No. 13, and PURSUIT, an imidazolinone herbicide, No. 6. Test conditions were the same as those in Examples 43-46. Test data are shown in Table 46. Other procedures for applying herbicidal formulations are as described in Example 42. Herbicide No. Rate (Kg/Ha) Biocide No. Antidote No.
• MON-13900, MON-7400 and Antidote No. 33 showed good activity in safening the COUNTER 15G/PURSUIT interaction. Flurazole (No. 7) was less effective than the other safeners. All four antidotes provided some safening, weak to moderate, against the COUNTER 15G/OUST interaction. These particular antidote/insecticide/herbicide combinations appear more difficult to reduce corn injury than the other combinations.
• COUNTER 15G is abbreviated as "C” and the antidotes as “A” in the column headings which indicate the "C + A” ratios used in the tests.
• Control and COUNTER treatments are average of four (4) replications and COUNTER + Antidote treatments, average of 2 reps.
• Benzhydryl antidotes MON-7400 and Antidote No. 51 were similar to MON-13900 for safening COUNTER 15G/BEACON negative synergy. Significant safening was seen with C:A ratios of 5-160. Antidote No. 16 was not as active as the other safeners in the test.
• test procedure in this example was according to Procedure VII and followed the description in Example 48.
• Test data shown in Table 48 represent the average of two replications. Again, in the table “C” stands for COUNTER” and A” for "Antidote”.
• BEACON® Kg/Ha
• In-Furrow Treatment C ⁇ A C:A Ratio % Inhibition Corn 0.28 - - 0 0.28 C - 55 0.28 C + 78 20 5 0.28 C + 78 40 5 0.28 C + 78 80 20 0.28 C + 78 160 20 0.28 C + 79 20 0 0.28 C + 79 40 5 0.28 C + 79 80 15 0.28 C + 79 160 20 0.28 C + 8 20 0 0.28 C + 8 40 0 0.28 C + 8 80 5 0.28 C + 8 160 15 0.28 C + 16 20 10 0.28 C + 16 40 20 0.28 C + 16 80 20 0.28 C + 16 160 25 0.28 C + 1 20 5 0.28 C + 1 40 5 0.28 C + 1 80 10 0.28
• MON-7400 Antidote No. 8 was similar to that of MON-13900 (No. 1) and CGA-154281 (No. 28) for protecting corn from COUNTER/BEACON injury. Acceptable corn injury was observed with COUNTER:Antidote ratios of 20 to 160. Comparable results were seen with COUNTER/ACCENT combinations, except that MON-13900 and CGA-154281 were more effective than MON-7400 at the 160 ratio. Antidote No. 16 was weak in safening effect in these tests.
• test procedure in this example was according to Procedure V described above.
• the herbicides were applied POE five (5) days after PPI initiation of biocide and antidote incorporation; observations were made nine (9) days later. Test results are shown in Table 50.
• Example 51 The test in this example paralleled that in Example 51, except the procedure was according to Procedure IV above and the herbicides used were No. 1 (MON-12000); No. 21 (XRD-498) and, again, No. 18 (PURSUIT); the biocide was, again, MOCAP®. Observations were taken thirteen (13) days after PPI treatment with biocide and antidote. Results are shown in Table 51. Herbicide No. Rate (Kg/Ha) Biocide No. 8 (kg/Ha) Antidote No.
• MOCAP applied alone caused significant corn injury (leaf malformations, stunting and stand reduction), which was enhanced by the addition of each of the herbicides.
• the antidote activity in this test ranged from moderate to nil, a probable consequence of MOCAP phytotoxicity.
• test safeners all provided moderate to high degrees of safening activity against interactions from combinations of FORTRESS with MON-12000 and XRD-498. With the exception of MON-7400, these antidotes were less effective against the FORTRESS/PURSUIT interaction.
• the herbicide was BEACON® (No. 8) in combination with co-herbicides H (2,4-D); F (BANVEL®); G (BLADEX®); I (MON-12000) or J (XRD-498).
• BEACON and XRD-498 were formulated in 50% water/50% acetone containing 0.25 v/v% of X-77 surfactant.
• the POE combinations were applied as tank mixtures, five (5) days after the PPI operation and plant response observations taken eight (8) days later. Test results are shown in Table 55.
• MON-7400, flurazole, MON-13900 or MON-4660 (Antidote No. 16, also has the code No. AD-67) applied in furrow, reduced corn injury from the interaction of COUNTER 15G with each of herbicide/co-herbicide combinations.
• Example 56 The test in this example was conducted in the manner described in Example 56, except substituting ACCENT® for BEACON as the primary herbicide (in the context of this invention) and observing results seven (7) days after POE herbicide application. Results are shown in Table 56.
• Herbicide No. Herbicide No.
• corn injury was reduced by in-furrow treatments of all herbicide/co-herbicide combinations applied POE and in contact with COUNTER 15G with all test antidotes.
• the procedure used in this example involved the PPI application of biocide and safener as described in general Procedure VI above.
• the "primary" herbicide in this test was MON-12000 (Herbi-cide No. 1) in admixture with other herbicides designated as "co-herbicides", which included LASSO® (co-herbicide B); DUAL® (C); acetochlor (A); EPTAM® (D); butylate (E) and PURSUIT® (K).
• MON-7400 was the most effective safener in this test followed by MON-13900, MON-4660 and flurazole.
• the herbicide PURSUIT® was used as the primary herbicide (in the context of this invention) together with the same insecticide and safeners as above and the co-herbicides shown in Table 60, together with test results.
• Tests according to this invention in various crops indicate widespread application of the invention.
• Examples 62-66 below are described tests with a variety of herbicides contacted with COUNTER® 15G in the presence and absence of MON-7400 (Antidote No. 12); MON-13900 (No. 1); MON-4660 (No. 16) and flurazole (No. 16).
• MON-7400 Antidote No. 12
• MON-13900 No. 1
• MON-4660 No. 16
• flurazole No. 16
• Plants used in all tests were, for crops (as abbreviated in parentheses); cotton (COTT); soybean (SOBE); CORN, grain sorghum (GRSO); wheat (WHEA) and RICE, and the weeds giant foxtail (GIFT) and velvetleaf (VELE).
• the data in the tables below represent averages of two replications.
• Example 62 The test procedure described in Example 62 was repeated using ACCENT® (Herbicide No. 7) as the herbicide; the biocide and safeners were the same. Test results are shown in Table 62.
• Herb. No. 7 Kg/Ha
• Biocide No. 1 Kg/Ha
• COUNTER and PURSUIT interacted negatively at one or more application rates to cause enhanced injury in corn, wheat and rice. Slight to moderate safening of corn was observed. Safening of weak interactions in wheat and rice ranged from slight to nil, depending on the antidote.
• the herbicidal component was MON-12000 (No. 1); the other components were the same.
• the procedure used in this test was the same as that described in Example 62, modified to use a light overhead irrigation (about 0.32 cm/day) during days 4-7 of the test. Results are shown in Table 64.
• XRD-498 Herbicide No. 21 was used as the herbicidal component in contact with COUNTER 15G in the presence of the above safeners.
• the various components of the system biocide, herbicide and safener were applied concurrently to soil covers of the seeded plants. Test results are shown in Table 65.
• Example 65 and 66 showed that increased injury to corn and wheat occurred as a result of the interaction between COUNTER 15G and MON-12000. All four safeners provided good protection against corn injury. With the exception of Antidote No. 33, the test antidotes showed good wheat safening.
• COUNTER 15G The combination of COUNTER 15G with the sulfonamide herbicide XRD-498 caused severe interactions with enhanced injury to corn and wheat. That injury was corrected to varying degrees by the antidotes. COUNTER 15G/XRD-498 negative synergy was also seen with cotton, grain sorghum and rice.
• the data in the above tables reflect the fact that interactions between insecticides and herbicides are susceptible to having their phytotoxicity to crops reduced by antidotal (safener) compounds, while still providing control or suppression of weeds.
• the data also reflect the common occurrence that the safening effect on various herbicides by safeners will have different degrees of effect depending upon a variety of factors, including, relative concentrations of herbicides and/or co-herbicides and/or antidotes, weather and soil conditions, water content, etc., as well appreciated in the art.
• compositions of this invention may contain at least one active ingredient and an adjuvant in liquid or solid form.
• the compositions are prepared by admixing the active ingredient with an adjuvant including diluents, extenders, carriers, and conditioning agents to provide compositions in the form of finely-divided particulate solids, granules, pellets, solutions, dispersions or emulsions.
• an adjuvant such as a finely-divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination of these.
• Suitable wetting agents are believed to include alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols, polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol and nonylphenol) and polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides (e.g., sorbitan).
• alkyl benzene and alkyl naphthalene sulfonates sulfated fatty alcohols, amines or acid amides
• long chain acid esters of sodium isothionate esters of sodium
• Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate, and polymethylene bisnaphthalene sulfonate.
• Wettable powders are water-dispersible compositions containing one or more active ingredients, an inert solid extender and one or more wetting and dispersing agents.
• the inert solid extenders are usually of mineral origin such as the natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such extenders include kaolinites, attapulgite clay and synthetic magnesium silicate.
• the wettable powders compositions of this invention usually contain from above 0.5 to 60 parts (preferably from 5-20 parts) of active ingredient, from about 0.25 to 25 parts (preferably 1-15 parts) of wetting agent, from about 0.25 to 25 parts (preferably 1.0-15 parts) of dispersant and from 5 to about 95 parts (preferably 5-50 parts) of inert solid extender, all parts being by weight of the total composition. Where required, from about 0.1 to 2.0 parts of the solid inert extender can be replaced by a corrosion inhibitor or anti-foaming agent or both.
• compositions include dust concentrates comprising from 0.1 to 60% by weight of the active ingredient on a suitable extender; these dusts may be diluted for application at concentrations within the range of from about 0.1-10% by weight.
• Aqueous suspensions or emulsions may be prepared by stirring a nonaqueous solution of a water-insoluble active ingredient and an emulsification agent with water until uniform and then homogenizing to give stable emulsion of very finely divided particles.
• the resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that when diluted and sprayed, coverage is very uniform.
• Suitable concentrations of these formulations contain from about 0.1-60%, preferably 5-50% by weight of active ingredient, the upper limit being determined by the solubility limit of active ingredient in the solvent.
• Concentrates are usually solutions of active ingredient in water-immiscible or partially water-immiscible solvents together with a surface active agent.
• Suitable solvents for the active ingredient of this invention include dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons, and water-immiscible ethers, esters, or ketones.
• other high strength liquid concentrates may be formulated by dissolving the active ingredient in a solvent then diluting, e.g., with kerosene, to spray concentration.
• the concentrate compositions herein generally contain from about 0.1 to 95 parts (preferably 5-60 parts) active ingredient, about 0.25 to 50 parts (preferably 1-25 parts) surface active agent and where required about 5 to 94 parts solvent, all parts being be weight based on the total weight of emulsifiable oil.
• Granules are physically stable particulate compositions comprising active ingredient adhering to or distributed through a basic matrix of an inert, finely-divided particulate extender.
• a surface active agent can be present in the composition.
• Natural clays, pyrophyllites, illite, and vermiculite are examples of operable classes of particulate mineral extenders.
• the preferred extenders are the porous, absorptive, preformed particles such as preformed and screened particulate attapulgite or heat expanded, particulate vermiculite and the finely-divided clays such as kaolin clays, hydrated attapulgite or bentonitic clays. These extenders are sprayed or blended with the active ingredient to form the herbicidal granules.
• the granular compositions of this invention may contain from about 0.1 to about 30 parts by weight of active ingredient per 100 parts by weight of clay and 0 to about 5 parts by weight of surface active agent per 100 parts by weight of particulate clay.
• compositions of this invention can also contain other additaments, for example, fertilizers, other herbicides, other pesticides, safeners and the like used as adjuvants or in combination with any of the above-described adjuvants.
• Chemicals useful in combination with the active ingredients of this invention included, for example, triazines, ureas, sulfonylureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acid and its derivatives, nitriles, biphenyl ethers, nitrobenzenes, etc.
• Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea, potash and superphosphate.
• Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.
• the practice of this invention comprises the use of the antidotal compounds disclosed and claimed herein with any herbicidally-active azolopyrimidine sulfonamide or derivative compound which may optionally be combined with co-herbicides from many different classes of chemistry.
• any herbicidally-active azolopyrimidine sulfonamide or derivative compound which may optionally be combined with co-herbicides from many different classes of chemistry.
• the above listings of exemplary compounds is not intended to be exhaustive, but representative.
• it is expected that not every combination of herbicide, insecticide and antidote will result in safening of all crops, but it is within the skill of the art to test any given herbicide/insecticide combination with an invention antidote in plant screens of any spectrum of plants and note the results.
• the herbicide, insecticide, antidote, or a mixture thereof may be applied to the plant locus without any adjuvants other than a solvent.
• these mixtures may be in the form of emulsifiable concentrates, microencapsulates, particulate solids, granules of varying particle size, e.g., water-dispersible or water-soluble granules or larger dry granules, pellets, wettable powders, dusts, solutions, aqueous dispersions, emulsions or other formulation types conventional in the art.
• Suitable adjuvants are finely-divided solid carriers and extenders including talcs, clays, pumice, silica, diatomaceous earth, quartz, Fuller's earth, sulfur, powdered cork, powdered wood, walnut flour, chalk, tobacco dust, charcoal, and the like.
• Typical liquid diluents include Stoddard's solvent, acetone, methylene chloride, alcohols, glycols, ethyl acetate, benzene, and the like.
• Liquids and wettable powders usually contain as a conditioning agent one or more surface-active agents in amounts sufficient to make a composition readily dispersible in water or in oil.
• surface-active agent includes wetting agents, dispersing agents, suspending agents, and emulsifying agents. Typical surface-active agents are mentioned in U.S. Patent No. 2,547,724.
• compositions of this invention generally may contain from about 5 to 95 parts herbicide-insecticide-and-antidote, about 1 to 50 parts surface-active agent, and about 4 to 94 parts solvent, all parts being by weight based on the total weight of the composition.
• the crop may be protected by treating the crop seed with an effective amount of antidote prior to planting. Generally, smaller amounts of antidote are required to treat such seeds. A weight ratio of as little as 0.6 parts of antidote per 1000 parts of seed may be effective. The amount of antidote utilized in treating the seed may be increased if desired. Generally, however, a weight ratio of antidote-to-seed weight may range from 0.1 to 10.0 parts of antidote per 1000 parts of seed.
• the compound preferably is formulated as an organic solution, powder, emulsifiable concentrate, water solution, or flowable formulation, which can be diluted with water by the seed treater for use in seed treating apparatus. Under certain conditions, it may be desirable to dissolve the antidote in an organic solvent or carrier for use as a seed treatment or the pure compound alone may be used under properly controlled conditions.
• suitable carriers may be either solids, such as talc, sand, clay, diatomaceous earth, sawdust, calcium carbonate, and the like, or liquids, such as water, kerosene, acetone, benzene, toluene, xylene and the like, in which the active antidote may be either dissolved or dispersed.
• Emulsifying agents are used to achieve a suitable emulsion if two immiscible liquids are used as a carrier.
• Wetting agents may also be used to aid in dispersing the active antidote in liquids used as a carrier in which the antidote is not completely soluble.
• Emulsifying agents and wetting agents are sold under numerous tradenames and trademarks and may be either pure compounds, mixtures of compounds of the same general groups, or they may be mixtures of compounds of different classes.
• Typical satisfactory surface active agents which may be used are alkali metal higher-alkylarylsulfonates such as sodium dodecylbenzenesulfonate and the sodium salts of alkylnaphthalenesulfonic acids, fatty alcohol sulfates such as the sodium salts of monoesters of sulfuric acid with n-aliphatic alcohols containing 8-18 carbon atoms, long-chain quaternary ammonium compounds, sodium salts of petroleum-derived alkylsulfonic acids, polyethylene sorbitan monooleate, alkylaryl polyether alcohols, water-soluble lignin sulfonate salts, alkali casein compositions, long-chain alcohols usually containing 10-18 carbon atoms, and condensation products of ethylene oxide with fatty acids, alkylphenols and mercaptans.
• alkali metal higher-alkylarylsulfonates such as sodium dodecylbenzenesulfonate and the sodium salts of alky
• the invention herein has been specifically exemplified with the herbicidal compounds identified above as Herbicide Nos. 1-28, co-Herbicides A-K, including several commercial herbicides, as representative of the herbicidal component; with Insecticide Nos. 1-10 as the biocidal component and by a wide variety of antidotes from multiple classes of chemistry, including, inter alia, numerous preferred dichloroacetamide antidote as representative of the compounds according to Formulae V and VI. It is to be understood that other compounds within the scope of the above formulae and other chemical classes are specifically contemplated as within the scope of this invention either as the herbicidal component or as a co-herbicide. For example, other triazolopyrimidine - and imidazolopyrimidine sulfonamides and their derivatives contemplated herein include the compounds described in the following U.S. patents and EP applications as relevant to the compounds of Formula I:
• herbicidal compounds used alone and/or as co-herbicides herein are intended merely as exemplary of the classes of herbicides which they represent.
• many other herbicidal compounds analogous to those represented herein having a variety of equivalent radicals substituted on the central nucleus may similarly be safened to various crop plants to a greater or lesser extent with the antidotal compounds of this invention.
• other ⁇ -haloacetamide and ⁇ -haloacetanilide compounds useful as herbicides or co-herbicides herein are described in U.S.
• heterocycyl phenyl ethers especially pyrazolyl aryl ethers
• pyrazolyl aryl ethers Herbicidally-useful heterocycyl phenyl ethers (especially pyrazolyl aryl ethers) are described, e.g., in U.S. Patent 4,298,749.
• Herbicidal diphenyl ethers and nitrophenyl ethers include 2,4-dichlorophenyl 4'-nitrophenyl ether ("nitrofen”), 2-chloro-1-(3'-ethoxy-4'-nitrophenoxy)-4-trifluoromethylbenzene (“Oxyfluorfen”), 2',4'-dichlorophenyl 3-methoxy-4-nitrophenyl ether (“Chlormethoxynil”), methyl 2-[4'-(2'', 4''-dichlorophenoxy)-phenoxy]-propionate, N-(2'-phenoxyethyl)-2-[5'-(2''-chloro-4-''-trifluoromethylphenoxy)-phenoxy]-propionamide, 2-methoxyethyl 2-[nitro-5-(2-chloro-4-trifluoromethylphenoxy)-phenoxyl-propionate and 2-chloro-4-trifluoromethylphenyl
• herbicidal ureas include 1-(benzothiazol-2-yl)-1,3-dimethylurea; phenylureas, for example: 3-(3-chloro-p-tolyl)-1,1-dimethylurea ("chlorotoluron”), 1,1-dimethyl-3-( ⁇ , ⁇ , ⁇ -trifluoro-m-tolyl)urea ("fluometuron”), 3-(4-bromo-3-chlorophenyl)-methoxy-1-methylurea (“chlorbromuron”), 3-(4-bromophenyl)-1-methoxy-1-methylurea ("metobro- muron”), 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea ("linuron”),
• herbicidal sulfonylureas and sulfonamides specifically contemplated as useful as the herbicidal component herein and/or a co-herbicides in compositions with the antidotal compounds of this invention include those disclosed in the following patents: U.S.
• herbicidal imidazolinone, imidazolidinethione and imidazolidinone or -dione compounds useful as the herbicidal component within the purview of this invention or as co-herbicides which may be safened for use in various crops include compounds disclosed in the following exemplary publications: EP Application Numbers 436483, 041623, 133310, 198552, 216360 and 298029; JA 1109-790, JA 1197-580A, J6 1183-272A and J6 3196-750A; and Australian published Application No. AU 8661-073A, GB 2 172 886A and U.S.
• herbicidal compounds contemplated for combination with the herbicidal and insecticidal components and with the antidotes of this invention include the following representative species:
• aryloxy- and ⁇ -(phenoxyphenoxy)-propionic acid derivatives and ⁇ -pyridyl-2-oxyphenoxy)-propionic acid derivatives are also aryloxy- and ⁇ -(phenoxyphenoxy)-propionic acid derivatives and ⁇ -pyridyl-2-oxyphenoxy)-propionic acid derivatives.
• An exemplary herbicide in the latter class is propionic acid, 2-[4-(3-fluoro-5-chloropyridin-2-yloxy)phenoxy] propynyl ester (code number CGA-184927).
• heteroaromatic oxyphenoxypropionic acid esters include those of 1,3-benzoxazoloxyphenoxypropionic acid and ester derivatives, typified by ( ⁇ )2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionic acid ethyl ester (common name "fenoxaprop-ethyl").
• herbicidal compounds useful as co-herbicides herein include aromatic and heterocyclic di- and triketones exemplified in U.S. Patent Nos. 4,797,147, 4,853,028, 4,854,966, 4,855,477, 4,938,796 and 4,869,748 and N-benzoyl-N-phenylalanine and its derivatives.
• pyrrolidinones e.g, the 1-phenyl-3-carboxyamidopyrrolidinones disclosed in U.S. Patent 4,874,422, and the 1-phenyl-4-haloalkylpyrrolidones disclosed in U.S. Patent 4,515,627, etc.
• herbicidal compounds useful as co-herbicides herein include benzoic acid derivatives of the type exemplified by 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitrobenzoic acid (“Acifluorfen”), 2,6-dichlorobenzonitrile (“dichlobenil”), 3,6-dichloro-2-methoxybenzoic acid (“dicamba”), etc. and compounds disclosed in U.S Patents 3,013,054, 3,027,248 and 3,979,437, etc.
• herbicidal compounds suitable for use herein includes benzothiadiazin-4-(3H)-one-2,2-dioxide and its derivatives, exemplified by 3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide (common name "bentazon").
• antidotal compounds contemplated as suitable herein include 1-(5-chloro-isoquinon-8-yloxy)-1-methylhexyl acetate (Code No. CGA-185072), a safener for CGA-184927 herbicide in wheat, and 3-[(2,4-dichlorophenyl]2-(trichloromethyl)-5-(ethoxycarbonyl)-triazol-3-yl (Code No. HOE 70541), a safener also for use in wheat.

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